Vat dyestuffs



United States Patent 3,300,491 VAT DYESTUFFS Walter Jenny, 'Istvan Hari,Max Staeuble, and Kurt Weber, Basel, Switzerland, assignors to CibaLimited, Basel, Switzerland, a Swiss company No Drawing. Filed May 21,1962, Ser. No. 196,433 Claims priority, application Switzerland, June 2,1961, 6,485/ 61; Apr. 2, 1962, 3,967/62 6 Claims. (Cl. 260-249) Thepresent invention provides new vat dyestuffs that in their moleculecontain at least one grouping of the formula in which R represents ahalogen-alkyl group, especially a halogen-alkyl group containing atleast 2 carbon atoms in the alkyl grouping, in which grouping thehalogen atom is attached to a terminal carbon atom. R advantageouslyrepresents the radical of the formula CH CH Halogen in which halogen mayrepresent a bromine atom, but more especially a chlorine atom. The termvat dyestuffs includes dyestuffs which are capable of conversion byreduction into a so-called leuco form or vat which has better aflinityfor natural and regenerated cellulose fibers than has the non-reducedform, and which can be reconverted by oxidation into the originalchromophoric system. As suit-able vat dyestuffs there may be mentionedmore especially those of the anthraquinone series, for example, thosewhich contain an unchanged 9:10- dioxoanthracene ring, and also thoseanthraquinones that also contain fused on carbocyclic or heterocyclicrings or which consist of several anthraquinone units, as well as vatdyestuffs of the perylene tetracarboxylic acid series, the naphthalenetetracarboxylic acid series, the pyrenequinone series, and indigoid vatdyestuffs. In addition to at least one grouping of the Formula 1 thedyestuffs may also contain the substituents usual in vat dyestuffs, forexample, halogen atoms, alkoxy groups, acylamino groups or 'alkylgroups. In certain cases the presence of hydrophilic groups can also beof advantage. The new dyestuffs are obtained when (a) a vat dyestuffthat contains an exchangeable halogen atom, for example, a vat dyestuffthat contains a sulfonic acid halide group, is condensed with an aminethat contains a substituent SO R or SR, in which R has the meaning givenabove, or (b) a vat dyestuff that contains at least one hydroxyalkylsulfonyl group or hydroxyalkyl sulfido group is treated withchlorinating agents, or (c) an aminoanthraquinone is reacted with anacylating agent that contains a halogen alkylsulfido radical or ahalogen alkylsulfone radical, especially one of the formula As startingmaterials for method (a) of the present process there are preferablyused vat dyestuffs that contain at least one sulfonic acid chloridegroup. Of special interest are vat dyestuffs that contain two suchgroups. As examples of suitable starting materials there may bespecially mentioned those of the anthraquinone series:1:5-dibenzoylamino anthraquinonedisulfochloride,dibenzanthrone-disulfochloride, isodibenzanthronedisulfochloride, andthe sulfochlorides of anthanthrone, dibenzpyrenequinone, pyranthrone,acedianthrone, flavanthrone, indanthr-one, N:N'-diethyl-dipyrazoleanthronyl, N:N-diisopropyldipyrazole anthronyl, anthraquinone-Z: 1 (N)1' 2'-(N)-naphthacridone, 1: l'-dianthrimide carbazole, and 2.:2"diphenyl anthraquinone-1:2(N)- 5 7 (N) dithiazole.

In addition to the sulfochlorides of the anthraquinone series alreadymentioned, there may also be used sulfochlorides of indigoid vatdyestuffs or of perylene tetracarboxylic acid diimides or of perinonedyestuffs. The aforesaid sulfochlorides can be obtained by treating theappropriate vat dyestuffs with chlorosulfonic acid, if necessary withpartial hydrolysis of the polysulfochlorides so obtained, or by reactingthe appropriate sulfonic acid With acid-halogenating agents, such asphosphorus halides, thionyl chloride or chlorosulfonic acid by knownmethods. Another method of obtaining the sulfochlorides that are toserve as starting materials consists in acylating amino-anthraquinoneswith benzoic acid-sul-fonic acid dichloride, in which process achlorosulfonyl-benzoylamino-anthraquinone is formed. In method (a) ofthe present process there are also used as starting materials thereaction products of aminoanthraquinones with halogen-pyrimidines orhalogentriazines, such as cyanuric chloride, that contain at least oneexchangeable chlorine atom, for example, a compound of the formula /N\ oNHC o-o1 I! l I II N N f 01 These are reacted with an amine thatcontains a p-halogen-alkylsulfone group or a ,B-halogenalkyl sulfidegroup, for example, with the amine of the formula or with an amine ofthe formula The reaction of the vat dyestuffs that contain exchangeablehalogen atoms, for example, the reaction of the aforesaid sulfochlorideswith the amine that contains a sub stituent -SO R or SR can be carriedout in an inert organic solvent, for example, nitrobenzene,chlorobenzene or ortho-dichlorobenzene at a raised temperature. However,since the sul-fochlorides are generally obtained in aqueous suspensionwhen they are prepared, it is of advantage to carry out the reactionwith the amine in aqueous medium, advantageously in the presence of anagent capable of binding acid, for example, sodium acetate, sodiumhydroxide or sodium carbonate. The molar ratios of the components areadvantageously chosen in such a manner that at least one mol of amine isused for each sulfochloride group of the vat dyestuff.

The starting materials for method (b) of the present process areadvantageously anthraquinone vat dyestuffs that contain one or twohydroxyalkyl'sulfone groups or hydroxy-alkyl sulfide groups,advantageously a group of this kind that contains at least two carbonatoms, such as the fl-hydroxyethyl-sul'fone groups or thefi-hydroxyethylsulfide groups, for example, the mono-or=di-B-hydroethylsulfones of 1:S-dibenzoylaminoaanthraquinone, ofdibenzanthrone or of i-sodibenzanthrone as well as thehydroxyethyl-sulfiones or hydroxyethyl-su lfides of anthanthrone,dibenzpyrene quinone, pyranthrone, acedianthrone, flavanthrone,indanthrone, N:N'-diethyldipyrazole anthronyl, N,N'diisopropyldipyrazoleanthronyl, anthraquinone-2:1(N) l2(N) naphthacridone, l:l'-dianthnimi-decarbazole, and 2:2"-diphenylanthraquinone-1:2- (N)-dithiazole. Inaddition to the aforesaid B-hydroxyethyl-sulfones or sulfides of theanthraquinone series, there may also be used sulfones or sulfides ofindigoid vat dyestulfs, perylenetetracarboxylic acid diimides or ofperinone dyestuffs. The fl-hyd'roxyethyl-sulfones or sulfides definedabove canbe obtained by reacting the appropriate sulfinates ormercaptans with chlonoethyl alcohol, or by reacting a vat dyestuff thatcontains exchangeable halogen atoms, for example, a vat dyestuffsulfonic acid halide or an amino-anthraquinone, to the amino group ofwhich a chlorotriazine radical is attached, with an amine of the formulaS-CHzCHr-OH HzN- As starting materials for method (c) of the presentprocess there may be used amino-anthraquinones, for example,1:S-diaminoanthraquinones, 1amino-5-benzoylaminoanthraquinone, 4-arninoanthraquinone 2:l(N)- acridone, 4:4'-, 4:5'- or 5:5'-diarnino-l:l'-dianth1rirnide carbazole.

As acylating agents that contain a halogen-alkyl-sulfone radical theremay be mentioned in particular benzoic acid halides, advantageouslythose of the formulae in which R represents a benzene radical. The saidacylating agents are advantageously obtained by reacting the appropriatehydroxy-ethyl-sulfonyl acids or hyd-roxyethyl-sulfide benzoic acids withacid-chlorinating agents, such as thionyl chloride. Likewise suitable asacylating agents are, for example, compounds of the formula The reactionof the aminosanthraquinones with the acylating agent is carried outadvantageously in an inert organic solvent, for example, nitmobenzene,chloro'benzene or ortho-dichlorobenzene, at a raised temperature. Themolar ratios of the components are advantageously chosen in such amanner that there is approximately one car- 'boxylic acid chloride groupor a group of the formula of the acylatring agent for each amino groupof the anthraquinone radical.

The dyestulfs so obtained can be isolated from the mixture in which theyhave been prepared and, notwithstanding the presence of the reactivegrouping of the Formula 1, can be worked up into useful dry dyestutfpreparations. The isolation is advantageously carried out by filtration.The filtered dyestuffs can be dried, if desired, after the addition ofbuffers or neutral or weakly alkaline extenders; drying isadvantageously carried out at not too high a temperature and, ifnecessary, under reduced pressure.

The new dyestuffs are suitable for dyeing a very wide variety ofmaterials, but especially for dyeing or printing textile materials ofnatural 'or regenerated cellulose by the usual vat dyeing or printingmethods. The dyeings and prints produced therewith are distinguished bytheir excellent fastness to light and excellent properties of wetfastness.

The dyeings produced with the dyestuffs of the invention are, in manycases, fast to dry cleaning and migration. The dyed fabrics cantherefore be coated with synthetic resins, for example, with polyvinylchloride, without the dyestuif migrating into the resin, which isparticularly important in the manufacture of artificial leather.

The dyestuffs of the invention can generally be vatted very easily,often at room temperature.

Unless otherwise stated, the parts and percentages in the followingexamples are by weight. The relationship of parts by weight to parts byvolume is the same as that of the gram to the cubic centimeter.

EXAMPLE 1 To 3.77 parts of 4-(i3-chloroethyl sulfonyl)-benzoylchloridein 50 parts of dry nitrobenzene is added, at C., a suspension of 2.3parts of 4:4'-diamino-1:1-dianthrimide carbazole in 38 parts ofnitrobenzene, and the whole is stirred for 6 hours at -145 C. and for 2hours at -175 C. After cooling the reaction mixture, the dyestuif, whichprecipitates in crystalline form, is isolated by filtration, washedsuccessively with nitrobenzene and hot alcohol, and dried in vacuo at 70C.

In the dry state, the dyestuff so obtained is in the form ofolive-colored crystals and dyes cotton and regenerated cellulose, forexample, by the process described in the last paragraph of this example,olive grey tints possessing very good properties fastness If, in thisexample, 5:5'-diamino-1:1'-dianthrimide carbazole is used instead of4:4-diamin0-1:1-dianthrimide carbazole, a dycstulf is obtained whichdyes cellulosic fibers brown tints which possess excellent properties ofWet fastness.

Fabrics dyed and printed with the dyestuffs so obtained can be coatedwith synthetic resins, for example, with plasticised polyvinyl chloride,without the dyestuif migrating into the resin, which is particularlyimportant in the manufacture of artificial leather.

14 parts of the dyestuif obtained as described in the first paragraph ofthis example are finely ground in a ball mill for 24 hours With 126parts of a neutral solution of 125 parts of dinaphthylmethane disulfonicacid in 1000 parts of water.

7.5 parts of the paste so obtained are suspended in 250 parts of warmwater. The dyestulf suspension so obtained is introduced into a solutionof 10 parts by volume of sodium hydroxide solution of 30% strength and 6parts of sodium dithionite in 1750 parts of water, the solution having atemperature of 50 C., and vatted for one minute. 50 parts of cotton aredyed for 45 minutes at 50-60 C. in the dyebath so obtained in thepresence of 60 parts of sodium chloride. After dyeing, the cotton isrinsed and soaped at the boil.

EXAMPLE 2 To a suspension of 7.35 parts of cyanurated l-amino-S-benzoylamino-anthraquhione of the formula oolml in 80 parts ofnitrobenzene and 8 parts of N:N-diethyl aniline are added, at 140 C.,3.5 parts of para-aminophenyl-(fi-chloroethyl)-sulfone of 95% strength.The whole is stirred for 6 hours at 140 C., cooled, and then slowlydiluted with a mixture of 80 parts of nitrobenzene, 250 parts of benzeneand 250 parts of ether. The dyestuff which is precipitated thereby, andwhich presumably has the formula is isolated by filtration, washed withether, and then dried in vacuo at 60 C. The dyestuif so obtained is ayellow powder which dyes cotton and regenerated cellulose fast yellowtints by the method described in Example 1.

EXAMPLE 3 To a fine suspension of 8.4 parts of cyanuratedaminoacediant-hrone in 100 parts of nitrobenzene and 8 parts ofdiethylaniline are added, at 140 C., 4.95 parts ofparaamino-phenyla(fi-chloroethyl)-sulfone. The whole is stirrred forhours at 130-135 C. and cooled. The dyestufi which is precipitatedthereby, and which presumably has the formula 6 is isolated byfiltration, well washed with ether, and then dried in vacuo at 65 to 70C. v

The dyestuff so obtained is a red-black powder which dyes cotton andregenerated cellulose very fast brown tints by the method described inExample 1.

EXAMPLE 4 5 parts of 1-amino-'5-bezoylamino-anthraquinone are dissolvedhot in 40 parts of ortho-dichlorobenzene and, to the solution soobtained, are added 3.45 parts of para- (fl-chloroeth-ylmencapto)-benZ0ylChloride. The solution so obtained is kept at the boilfor 10 minutes and then cooled. The dyestuff which is precipitatedthereby, and which has the formula NHC o-Os-omomor can be isolated byfiltration, washed with hot alcohol, and dried in vacuo at 65 to 70 C.The dyestufi crystallizes from ortho-dichlor-obenzene in the form oforangeyellow crystals and dyes cotton and regenerated cellulose yellowtints which are fast to washing when applied by the method described inExample 1.

EXAMPLE 5 5.1 parts of l(4'-amino-benzoylamino)-5-benzoylamino-anthraquinone are suspended inparts of nitrobenzene and, to the suspension so obtained, are added 2.6parts of meta-(B-chlOroet-hyl mercapto)-benzoylchloride. The suspensionso obtained is stirred for 30 minutes at C. and cooled. The dyestuifwhich is precipitated thereby, and which has the formula I S-CHzCHzC] 7EXAMPLE 6 4.1 parts of the dyestulf of the formula IIIHOSOrOHzOHzOH Care heated for 2 hours at 120 to 125 C., while stirring, in 33 parts ofnitrobenzene in the presence of 1.45 parts by volume of thionylchlorideand 0.3 part by volume of dimethylfonmamide. When the reaction mixturehas cooled, it is filtered, the filter cake is washed with ethanol anddried at 60 to 70 C. in vacuo. The dyestutf so obtained of the formuladyes cotton and regenerated cellulose fast yellow tints by the methoddescribed in Example 1.

8 EXAMPLE 7 1.25 parts of the dyestuif of the formula (l o lfiIH-O o- N/II o is an orange-yellow crystalline product that dyes cotton andregenerated cellulose pure yellow tints possessing good properties offastness when applied by the method described in Example -1.

The stanting dyestuif can be prepared as follows: To a solution of 1.8parts of amino-anthraquinone of the formula IOI NH:

in parts by volume of N-methyl-pyrrolidone are added at 120 C., 4.9parts of Z-phenyl-benzthiazole-6-carboxylic acid chloride, and the wholeis stirred for 3 minutes at 165 C. The reaction mixture is then cooledand diluted with 150 ml. of absolute ethanol. The dyestuff intermediateproduct that is precipitated thereby is isolated, boiled for a shortperiod in ml. of absolute ethanol, isolated and then dried.

EXAMPLE 8 A fine suspension of 3.0 parts of the dyestuff intermediateproduct of the formula 9 in 30 parts of nitrobenzene is sti-rred for 4hours at 125 C. in the presence of 0.7 part by volume of thionylchlorideand 0.15 part by volume of dimethylformarnide. The isolated dyestuff ofthe formula when in the dry state, is a dark red-brown product that dyescotton and regenerated cellulose bright red tints when applied by themethod described in Example 1. The starting dyestufi can be prepared asfollows:

A fine suspension of 3.25 parts of disulfochloride of the I formula Iand 2.47 parts of para-aminophenyl-(B-hydroxy-ethyl)- sulfone and 0.3part of anhydrous sodium carbonate in 50 parts of nitrobenzene and 8parts by volume, of N:N'- diethylaniline is stirred for 1 hour at 165 C.and cooled. The isolated dyestulf intermediate product is boiled up inethyl alcohol of 80% strength, separated from the alcohol and thendried. In the dry state it is a dark a brown powder that no longercontains chlorine.

EXAMPLE 9 2.24 parts of the condensation product of 2 mols of1-amino-anthraquinone with 1 11101 of cyanuric chloride are heated for16 hours at 175 C., while stirring, in parts of nitrobenzene in thepresence of 1.8 parts of paraamino-phenyl-(B-chloroethyl)-sulfone. Whenthe reaction mixture has been cooled, the dyestutf of the formula I ONH- O ITIH I o o V II I I p m N (n 7 ll II 0 0 is isolated, boiled upfor a short period in ethanol, isolated from the alcohol, and thendried. The\ dyestufi so obtained dyes cotton and regenerated cellulosepure yellow tints of high tinctorial strength when Iapplied by themethod described in Example 1. 1

EXAMPLE 10 1.8 parts of 1 (4' aminobenzoylamino)-5-benzoylamino-anthraquinone are suspended in parts ofnitrobenzene and, to this suspension, are added 1.1 parts of4-(fl-chloroethyl-sulfonyl)-benzoylchloride. The suspen sion so obtainedis stirred for 30 minutes at 165 C. and then cooled. The dyestuif of theformula which is isolated by filtration, is boiled for a short period inethanol, isolated by suction filtration, and dried. The dyestuif soobtained is a yellow crystalline product that dyes cotton andregenerated cellulose yellow tints possessing excellent properties offastness when applied by the method described in Example 1.

EXAMPLE 1 1 To a suspension of 3.7 parts of cyanurated l-amino-S-benzoylamino-anthraquinone of the formula t I O NH-C 0-01 11 I a 1 IIIHO oo 1T 12 in 40 parts of nitrobenzene and 4 parts of N:N-diethyl- 3.The vat dyestuif of the formula aniline are added, at 110 C., 1.5 partsof para-aminophenyl-(para-chloroethyl)-sulfide. The whole is stirred IYI0 N OC SO:OH2CH2C1 for 5 hours at 140 C., cooled, and then slowlydiluted with a mixture of 40 parts of benzene and 40 parts of 5 ether.The dyestuff of the formula EN 0 C oo 4. The vat dyestuff of the formulaII HN 0 NH-O/ O-NH- I1 0 C 0 1 II SOz-CHzCHrCl NH cs OO-NH whichprecipitates thereby is isolated by filtration, washed SOFCHMHFCI withether, and then dried in vacuo at 60 C. The dyestutf so obtained is ayellow powder that dyes cotton and regenerated cellulose fast yellowtints when applied by The Vat dyestuff of the formula the methoddescribed in Example 1.

What is claimed is: N 1. The vat dyestuff of the formula O N U n 1 O r6. The vat dyestuif of the formula 1}THO o-Osmomomcr ll HI:\I 0

NH I I 2. The vat dyestuff of the formula 1 NHOSOz-CH:CH:CI II V (I) 0NH OC-QSOKJHnCl-ECI 0 f fi References Cited by the Examiner -K UNITEDSTATES PATENTS N "2,992,240 '7/1961 Lodge 260271 X WALTER A. MODANCE,Primary Examiner.

I H U IRVING MARCUS, M. WESTERN, BOND, O 0 Examiners,

1. THE VAT DYESTUFF OF THE FORMULA